Note: Descriptions are shown in the official language in which they were submitted.
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HYDROPHILIC ETHER CARBOXYLIC ACIDS AS LUBRICANT FOR SALT
BASED DRILLING SYSTEMS
The present invention relates to a composition comprising (i) at least 10 wt%
of an
inorganic and/or organic, water soluble salt, based on the total weight of the
composition; (ii)
water; and (iii) an ether monocarboxylic acid. Further aspects of the
invention relate to the use
of an ether monocarboxylic acid of the invention, an amide, a salt or an ester
thereof as a
lubricant preferably in salt based drilling systems.
BACKGROUND OF THE INVENTION
Lubricants with improved biodegradability are desirable for example for
equipment used in
certain resource industries, such as forestry, mining, petroleum exploration
and production, in
particular wherever the lubricants themselves might come into contact with the
environment.
Drilling fluids or muds are commonly circulated in the well during drilling
operations in order
to cool and lubricate the drilling apparatus, lift cuttings out of the
wellbore and
counterbalance the subterranean formation pressure encountered during
drilling. An important
function of a drilling fluid is to reduce the considerable torque on the
rotating drill stem
caused by the friction between the outside of the drill pipe comprising the
drill stem and the
wall of the well and/or casing strings. Drilling through offsets, deep wells
and highly deviated
or horizontal wells results in increased frictional forces, increasing the
demand on the
lubricating properties of the drilling fluids.
The oil and gas industry has used brines for well drilling and well
completions for decades.
High density brines have been found to be particular applicable for example in
deep wells.
In particular during the operation of deep wells, as well as in extended reach
and/or high
angle wells, it is generally necessary for the brine-containing well treatment
fluid to exhibit
improved lubricity. The literature reports various additives for use as
lubricating agents in
drilling fluids as well as completion fluids, e.g. US 2010/016180 and DE 10
2005 060 459.
Many of the reported additives are not, however, compatible with clear brines
or drilling
fluids or completion fluids which have brine as a major component. In
addition, many
additives used as lubricating agents in drilling fluids and/or completion
fluids today have
presented environmental concerns and tend to be costly.
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Thus, a need exists for lubricating agents which may be used in brine-based
drilling fluids
and/or completion fluids. Such lubricating agents need to lower torque and
drag by reducing
metal to metal friction. Furthermore, they need to be useful in the prevention
of differential
sticking of downhole tubulars. Such lubricating agents further should be
environmentally
friendly.
It was therefore an object of the invention to provide a lubricant composition
which is
environmental friendly, is temperature and alkali stable and shows good
solubility in brine
based drilling fluids.
SUMMARY OF '1111, INVENTION
To solve the aforementioned problems the present invention provides in a first
aspect a
composition comprising
(a) at least 10 wt% of an inorganic and/or organic, water soluble salt,
based on the total
weight of the composition;
(b) water; and
(c) an ether monocarboxylic acid of the general formula (I), an amide, a salt
or an ester
thereof
R-0(CH )C1-110)x(CH2CHR10)yClTh-COOZ (I)
wherein
R is a saturated or unsaturated, branched or unbranched alkyl or alkenyl
radical having from 6
to 22 carbon atoms;
x is an integer number of at least 5;
y is an integer number between 0 and 3;
Rl is an alkyl radical having from 1 to 4 carbon atoms;
Z is a hydrogen atom or a monovalent or polyvalent cation.
Also provided is the use of an ether carboxylic acid according to the
invention as a lubricant.
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In preferred embodiments of the use according to the invention the ether
carboxylic acid said
amide, salt or ester thereof is used as a lubricant in a brine-based drilling
fluid, in a
completion fluid or in a workover fluid.
DETAILED DESCRIPTION OF THE INVENTION
Before the present invention is described in detail below, it is to be
understood that this
invention is not limited to the particular methodology, protocols and reagents
described herein
as these may vary. It is also to be understood that the terminology used
herein is for the
purpose of describing particular embodiments only, and is not intended to
limit the scope of
the present invention which will be limited only by the appended claims.
Unless defined
otherwise, all technical and scientific terms used herein have the same
meanings as commonly
understood by one of ordinary skill in the art.
In the following passages different aspects of the invention are defined in
more detail.
Each aspect so defined may be combined with any other aspect or aspects unless
clearly
indicated to the contrary. In particular, any feature indicated as being
preferred or
advantageous may be combined with any other feature or features indicated as
being preferred
or advantageous.
Some documents are cited throughout the text of this specification.
The term "water-soluble" is defined herein as a compound with a solubility in
distilled
water at 20 C of at least 33 g/1. Conversely, "water-insoluble" is any
compound that is not
"water soluble".
The present invention provides novel compositions, in particular lubricants.
It was
unexpectedly found that the ether monocarboxylic acid of the invention has
good lubricating
properties and improved biodegradability and is particularly suitable for use
in brine-based
drilling fluids. Similarly, also a derivative of the ether monocarboxylic acid
of the invention
such as an amide, a salt or an ester thereof is expected to share these
advantageous properties.
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Thus, in a first aspect the invention provides a composition comprising
(a) at least 10 wt% of an inorganic and/or organic, water soluble salt,
based on the total
weight of the composition;
(b) water; and
(c) an ether monocarboxylic acid of the general formula (I), an amide, a
salt or an ester
thereof
R-0(CH2CH20)7(CH2CHR10)yCH2-COOZ (I)
wherein
R is a saturated or unsaturated, branched or unbranched alkyl or alkenyl
radical having from 6
to 22 carbon atoms;
x is an integer number of at least 5;
y is an integer number between 0 and 3;
Ri is an alkyl radical having from 1 to 4 carbon atoms;
Z is a hydrogen atom or a monovalent or polyvalent cation.
In a preferred embodiment the composition comprises
(a) at least 15 wt% or at least 20 wt% of an inorganic and/or organic,
water soluble salt,
based on the total weight of the composition;
(b) water; and
(c) an ether monocarboxylic acid of the general formula (I), an amide, a
salt or an ester
thereof
R-0(CH2CH20)1(CH2CHR10)yCH2-COOZ (I)
wherein
R is a saturated or unsaturated, branched or unbranched alkyl or alkenyl
radical having from 6
to 22 carbon atoms;
x is an integer number of at least 5;
y is an integer number between 0 and 3;
R1 is an alkyl radical having from 1 to 4 carbon atoms;
Z is a hydrogen atom or a monovalent or polyvalent cation.
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The ester of said ether monocarboxylic acid in (c) is preferably a Cl -C8
alkyl ester or a Cl-
C8 alkenyl ester that may be optionally substituted for example with -OH, -NH,
or a
halide radical (such as Cl, Br, I, or F),
Said salt of the ether monocarboxylic acid in (c) is in one embodiment
preferably an amine
salt of said acid. If in a preferred embodiment component (c) is an amine salt
of said ether
monocarboxylic acid, then said salt preferably has a structure of general
formula (I) wherein Z
is preferably NH4, NH3R2+, NH2R2R3+ or NHR2R3R4+, wherein R2, R3 and R4 is
each
individually selected from a Cl-C8 alkyl or a C I-C8 alkenyl, each optionally
substituted with
-OH, -NH, or a halide radical (such as Cl, Br, I, or F). Alternatively, Z may
also be NH3,
NH2R, NHR2R3 or NR2R3R4, wherein R2, R3 and R4 is each individually selected
from a Cl-
C8 alkyl or a Cl -C8 alkenyl, each optionally substituted with -OH, -NH2 or a
halide radical
(such as Cl, Br, I, or F). Also other salts of said ether monocarboxylic acid
may be used in (c).
In such embodiments, Z may for example be selected from the group consisting
of sodium,
lithium, potassium, caesium, calcium, magnesium and zinc.
If as component (c) an amide of said ether monocarboxylic acid of the general
formula (I) is
used then this amide can have a structure according to the general formula
(11)
R-0(CH2CH2O)1(CH2CHR 0)yCH2-C(0)NR'R" (II)
wherein R, RI, x, y are as defined herein and
wherein R' and R" is each individually selected from the group consisting of
hydrogen, Cl-
C8 alkyl and C1-C8 alkenyl, each optionally substituted with -OH, -NH2, a
halide radical
(such as Cl, Br, I, or F), or -OCH3. In one preferred embodiment of the amide,
R' is
-CH2CH2OH and R" is H. In another preferred embodiment, R' and R" both are
-CH2CH2OH.
The inorganic, water soluble salt in (a) may be selected from the group,
consisting of alkali,
alkaline earth salt, and a transition metal, in particular selected from the
group consisting of
potassium, caesium, calcium, magnesium and zinc or mixtures thereof. Preferred
are the
halide salts thereof, in particular chloride or bromide. In particular
preferred salts are selected
from the group consisting of KC1, CsCl, NaC1, CaCl2, KBr and CaBr2.
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Preferred organic salts that can be used as component (a) are selected from
the group
consisting of a formiate (e.g CsCOOH or KCOOH), oxalate, nitrate, glycolate,
lactate and an
acetate.
In a preferred embodiment of the composition R is a radical according to
general formula (II)
or (III):
CH3(CH2)aCH=CH(Ct2)bCH9- (H)
CH3(CH2),CH=CH(CH ?),CH2- (III)
wherein
a and b are each individually selected from an integer of between 4 and 9 and
preferably of
between 6 and 7.
Preferably, the ether monocarboxylic acid of the invention, amide, salt or
ester thereof does
not form any substantial precipitates or other solid byproducts when added to
the components
(a) and (b), which would tend to increase the possibility of inadvertent drill
stem clogging
which could ultimately also cause formation damage. In the presence of
components (a) and
(b) the ether monocarboxylic acid or ester thereof of the invention is
preferably present in an
amount of no more than about 5 wt% and more preferably less than about 2.5 wt%
in solid
form, i.e. non-dissolved form based on the total weight of the composition.
Preferably, the turbidity of the composition according to the invention when
determined at
20 C using the ISO 7027:1999 turbidity method to measure the attenuation of a
radiant flux
does not exceed the sum of 100 formazin nephelometric units (FNU) plus the
turbidity of a
composition solely comprising components (a) and (b) and/or wherein the
composition does
not comprise any precipitated material.
Preferably, the composition according to the invention is a lubricant
composition and does not
comprise any water-insoluble lubricant.
In a further preferred embodiment, the composition according to the invention
is a lubricant
composition and does not comprise any additional lubricant besides said ether
monocarboxylic acid. In this context it is further preferred that the
composition does not
comprise as an additional lubricant any one or a combination of the following
compounds:
a) carboxylic acid esters of formula (II)
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R'-COO-R'' (II)
wherein R represents a saturated or unsaturated, linear or branched alkyl
radical having 5 to 23 carbon atoms and R" is an alkyl radical having 1 to 22
carbon atoms, wherein R" may be saturated or unsaturated, linear or branched;
b) fatty acids of the general formula (III)
R'"-COOX (III)
wherein R" is is a saturated, unsaturated, branched or unbranched alkyl or
alkenyl radical having from 5 to 23 carbon atoms and X is a hydrogen atom or
a mono- or polyvalent cation:
c) full or partial esters of glycerol with fatty acids of the above formula
(III);
d) a paraffin.
In a further preferred embodiment of the composition of the invention y = 0.
It is also
preferred that x is at least 9. In a more preferred embodiment y = 0 and x =
9.
It is also preferred that the composition according to the invention is not an
emulsion.
Preferably, the composition according to the invention is a composition
wherein R is a
saturated or unsaturated C12-C22 alkyl and even more preferably wherein R is a
saturated or
unsaturated C14-C20 alkyl.
The amount of inorganic and/or organic salt that may be comprised in the
composition of the
invention will depend on the type of salt that is being used and its
solubility in water. As
mentioned herein it is preferred that the amount of precipitated material is
kept small, for
example kept below a total amount of less than about 5 wt%. Using methods to
measure
turbidity the skilled artisan can adjust the salt amounts such that the amount
of precipitation
of said salt is suitable for the respective technical use that the composition
of the invention is
used for. Accordingly, in preferred embodiments, component (a), i.e. the
inorganic and/or
organic salt, is present in an amount from at least 10 wt.-% to about 85 wt.-
%, in particular,
from at least about 15 wt.-% to about 30 wt.-%.
Component (b), water, is preferably present in an amount of at least about 15
wt%, or at least
about 50 wt.-%, preferably at least about 70 wt.-%, in particular at least
about 80 wt.-%. The
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amount of water will typically be used to adjust the content of said salt and
ether
monocarboxylic acid or ester thereof in said composition.
Component (c), the ether monocarboxylic acid or ester thereof, is preferably
present in an
amount of at least about 0.1 wt.-% to at least about 10 wt.-%, preferably at
least about 0,15
wt.-% to about 5 wt.-%, in particular at least about 0,2 wt.-% to about 3 wt.-
%.
In a further preferred embodiment the composition of the invention further
comprises an
additive selected from the group consisting of a viscosity modifier, a pour
point depressant, a
flow improver, an anti-static agent, an ashless antioxidant, an antifoam
agent, a corrosion
inhibitor, an antiwear agent, a seal swell agent, an antimisting agent, a
water soluble lubricant,
an organic solvent, a gel-breaking surfactant and mixtures thereof.
In this context, the mentioned viscosity modifier is preferably selected from
the group
consisting of hydrogenated copolymers of styrene-butadiene, ethylene-propylene
copolymers,
polyisobutenes, hydrogenated styrene-isoprene polymers, hydrogenated isoprene
polymers,
polymethacrylates, polyacrylates, polyalkyl styrenes, alkenyl aryl conjugated
diene
copolymers, polyolefins, esters of maleic anhydride-styrene copolymers,
functionalized
polyolefins, ethylene-propylene copolymers functionalized with the reaction
product of
maleic anhydride and an amine, polymethacrylate functionalized with an amine,
styrene-
maleic anhydride copolymers reacted with an amine, polymethacrylate polymers,
esterified
polymers, esterified polymers of a vinyl aromatic monomer and an unsaturated
carboxylic
acid or derivative thereof, olefin copolymers, ethylene-propylene copolymer,
polyisobutylene
or mixtures thereof.
A water soluble lubricant may be for example an ester that is different from
component (c) of
the composition of the invention.
A gel breaking surfactant is preferably selected from the group consisting of
glycerol
monooleate, tall oil fatty acid, linoleic and stearic acids and derivatives
thereof, non-ionic
surfactants, and mixtures thereof.
Ashless antioxidants preferably include alkyl-substituted phenols such as 2,6-
di-tertiary butyl-
4-methyl phenol, phenate sulfides, phosphosulfurized terpenes, sulfurized
esters, aromatic
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amines, diphenyl amines, alkylated diphenyl amines and hindered phenols, bis-
nonylated
diphenylamine, nonyl diphenylamine, octyl diphenylamine, bis-octylated
diphenylamine, bis-
decylated diphenylamine, decyl diphenylamine and mixtures thereof. Hindered
phenols
include but are not limited to 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-
butylphenol, 4-
ethyl-2,6-di-tert-butylphenol, 4-propy1-2,6-di-tert-butyl phenol, 4-buty1-2,6-
di-tert-
butylphenol 2,6-di-tert-butylphenol, 4-penty1-2-6-di-tert-butylphenol, 4-hexy1-
2,6-di-tert-
butylphenol, 4-hepty1-2,6-di-tert-butylphenol, 4-(2-ethylhexyl)-2,6-di-tert-
butylphenol, 4-
octy1-2,6-di-tert-butylphenol, 4-nony1-2,6-di-tert-butylphenol, 4-decy1-2,6-di-
tert-butylphenol,
4-undecy1-2,6-di-tert-butylphenol, 4-dodecy1-2,6-di-tert-butylphenol, 4-
tridecy1-2,6-di-tert-
butylphenol, 4- le tradec y1-2,6-di-tert-butylphenol, methylene-bridged s
teric all y hindered
phenols include but are not limited to 4,4-methylenebis(6-tert-butyl-o-
cresol), 4,4-
methylenebi s (2-tert- amyl-o-cresol), 2,2-methylenebis(4-methyl-6-tert-
butylphenol),
methylene-bis(2,6-di-tertbutylphenol) and mixtures thereof. Another example of
an ashless
antioxidant is a hindered, ester-substituted phenol, which can be prepared by
heating a 2,6-
dialkylphenol with an acrylate ester under based conditions, such as aqueous
KOH. Ashless
antioxidants may be used alone or in combination. The antioxidants are
typically present in
the range of about 0 wt % to about 95 wt %, in one embodiment in the range
from about 0.01
wt % to 95 wt % and in another embodiment in the range from about 1 wt % to
about 70 wt %
and in another embodiment in the range from about 5 wt % to about 60 wt %
based on the
total weight of the lubricant composition.
Anti-wear agents include a sulfur or chlorosulphur extreme pressure (EP)
agent, a chlorinated
hydrocarbon EP agent, or a phosphorus EP agent, or mixtures thereof. Examples
of such EP
agents are amine salts of phosphorus acid, chlorinated wax, organic sulfides
and polysulfides,
such as benzyldisulfide, bis-(chlorobenzyl) disulfide, dibutyl tetrasulfide,
sulfurized sperm
oil, sulfurized methyl ester of oleic acid sulfurized alkylphenol, sulfurized
dipentene,
sulfurized terpene, and sulfurized Diels-Alder adducts; phosphosulfurized
hydrocarbons, such
as the reaction product of phosphorus sulfide with turpentine or methyl
oleate, phosphorus
esters such as the dihydrocarbon and trihydrocarbon phosphate, i.e., dibutyl
phosphate,
diheptyl phosphate, dicyclohexyl phosphate, pentyl ph en yl phosphate; di pen
tyl phen yl
phosphate, tridecyl phosphate, distearyl phosphate and polypropylene
substituted phenol
phosphate, metal thiocarbamates, such as zinc dioctyldithiocarbamate and
barium
heptylphenol diacid, such as zinc dicyclohexyl phosphorodithioate and the zinc
salts of a
phosphorodithioic acid combination may be used and mixtures thereof. In one
embodiment
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the antiwear agent/extreme pressure agent comprises an amine salt of a
phosphorus ester acid.
The amine salt of a phosphorus ester acid includes phosphoric acid esters and
salts thereof;
dialkyldithiophosphoric acid esters and salts thereof; phosphites; and
phosphorus-containing
carboxylic esters, ethers, and amides; and mixtures thereof. In one embodiment
the
phosphorus compound further comprises a sulfur atom in the molecule. In one
embodiment
the amine salt of the phosphorus compound is ashless, i.e., metal-free (prior
to being mixed
with other components). The amines which may be suitable for use as the amine
salt include
primary amines, secondary amines, tertiary amines, and mixtures thereof.
Antifoam agents include organic silicones such as poly dimethyl siloxane, poly
ethyl siloxane,
polydiethyl siloxane, polyacrylates and polymethacrylates, trimethyl-triflouro-
propylmethyl
siloxane and the like. An antifoam agent may be used in the range of about 0
wt % to about
wt %, in one embodiment in the range of about 0.02 wt % to about 10 wt % and
in another
embodiment in the range of 0.05 wt % to about 2.5 wt % based on the weight of
the lubricant
15 composition.
A suitable friction modifier may preferably be an organo-molybdenum compound,
including
molybdenum dithiocarbamate. In one embodiment, the friction modifier is a
phosphate ester
or salt including a monohydrocarbyl, dihydrocarbyl or a trihydrocarbyl
phosphate, wherein
20 each hydrocarbyl group is saturated. Each hydrocarbyl group may contain
from about 8 to
about 30, or from about 12 up to about 28, or from about 14 up to about 24, or
from about 14
up to about 18 carbons atoms. In another preferred embodiment, the hydrocarbyl
groups are
alkyl groups. Examples of hydrocarbyl groups include tridecyl, tetradecyl,
pentadecyl,
hexadecyl, heptadecyl, octadecyl groups and mixtures thereof. If the friction
modifier is a
phosphate salt, the phosphate salt may for example be prepared by reacting an
acidic
phosphate ester with an amine compound or a metallic base to form an amine or
a metal salt.
The amines may be monoamines or polyamines. In one embodiment, the friction
modifier is a
phosphite and may be a monohydrocarbyl, dihydrocarbyl or a trihydrocarbyl
phosphite,
wherein each hydrocarbyl group is saturated. In several embodiments each
hydrocarbyl group
may independently contain from about 8 to about 30, or from about 12 up to
about 28, or from
about 14 up to about 24, or from about 14 up to about 18 carbons atoms. In one
embodiment,
the hydrocarbyl groups are alkyl groups. Examples of hydrocarbyl groups
include tridecyl,
tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl groups and mixtures
thereof. In one
embodiment, the friction modifier is a fatty imidazoline comprising fatty
substituents
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containing from 8 to about 30, or from about 12 to about 24 carbon atoms. A
suitable fatty
imidazoline includes those described in U.S. Pat. No. 6,482,777. The friction
modifiers can be
used alone or in combination. The friction reducing agents are preferably
present in the range
of about 0 wt % to 60 wt %, or from about 0.25 wt % to about 40 wt %, or from
about 0.5 wt
% to about 10 wt % based on the total weight of the lubricant composition.
Said anti-misting agents include very high (>=100,000 Mn) polyolefins such as
1.5 Mn
polyisobutylene (for example the material of the trades name Vistanex(R)), or
polymers
containing 2-(N-acrylamido), 2-methyl propane sulfonic acid (also known as
AMPS(R)) or
derivatives thereof. The anti-misting agents can be used alone or in
combination. The anti-
misting agents are present in the range of about 0 wt % to 10 wt %, or from
about 0.25 wt %
to about 10 wt %, or from about 0.5 wt % to about 2.5 wt % based on the total
weight of the
lubricant composition.
The corrosion inhibitors that can be used according to the invention include
alkylated succinic
acids and anhydrides derivatives thereof, organo phosphonates and the like.
The corrosion
inhibitors may be used alone or in combination. The rust inhibitors are
present in the range of
about 0 wt % to about 20 wt %, and in one embodiment in the range from about
0.0005 wt %
to about 10 wt % and in another embodiment in the range from about 0.0025 wt %
to about
2.5 wt % based on the total weight of the lubricant composition.
The flow improvers mentioned in the context of the lubricant composition of
the invention
include ethylene vinyl acetate copolymers and the like. The flow improvers may
be used
alone or in combination. The flow improvers are preferably present in the
range of about 0 wt
% to about 50 wt %, or from about 0.0005 wt % to about 25 wt %, Of from about
0.0025 wt %
to about 5 wt % based on the total weight of the lubricant composition.
The pour point depressants include alkylphenols and derivatives thereof,
ethylene vinyl
acetate copolymers and the like. The pour point depressant may be used alone
or in
combination. The pour point depressant are for example present in the range of
about 0 wt %
to about 50 wt %, or from about 0.0005 wt % to about 25 wt %, or from about
0.0025 wt % to
about 5 wt % based on the total weight of the lubricant composition.
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The seal swell agents include organo sulfur compounds such as thiophene, 3-
(decyloxy)tetrahydro-1,1-dioxide, phthalates and the like. The seal swell
agents may be used
alone or in combination. The seal swell agents are for example present in the
range of about 0
wt % to about 50 wt %, or from about 0.0005 wt % to about 25 wt %, or from
about 0.0025
wt % to about 5 wt % based on the total weight of the lubricant composition.
In a preferred embodiment of the composition of the invention said ether
monocarboxylic
acid, amide, salt or ester thereof as defined herein is characterized by a
biodegradation rate
after 28 days of at least 60% CO2 formation relative to the theoretical value
of CO2 formation
as measured using a manometric tespirometry test according to OECD 301 B, ISO
9439,
92/69 / EEC.
In a further aspect the invention provides the use of an ether monocarboxylic
acid, an amide, a
salt or an ester thereof according to the invention as a lubricant.
Preferably, the ether monocarboxylic acid of the invention, amide, salt or
ester thereof is used
as a lubricant in a brine based drilling fluid, in a completion fluid or in a
workover fluid. As
used in this context "brine based" means that the drilling fluid can comprise
at least 10 wt%
of an inorganic and/or organic, water soluble salt such as those outlined
above. Thus, in a
further preferred embodiment of the use according to the invention, the brine
based drilling
fluid comprises at least 10 wt% inorganic and/or organic, water soluble salts,
based on the
total weight of the drilling fluid.
In a further preferred embodiment of the use according to the invention the
ether
monocarboxylic acid, amide, salt or ester thereof is used as the sole
lubricant in said brine
based drilling fluid.
In a further preferred embodiment, the ether monocarboxylic acid, amide, salt
or ester thereof
is used as lubricant in a brine based drilling fluid, in a completion fluid or
in a workover fluid,
wherein said brine based drilling fluid, completion fluid or workover fluid
does not comprise
any water-insoluble lubricants.
Various modifications and variations of the invention will be apparent to
those skilled in
the art without departing from the scope of the invention. Although the
invention has been
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described in connection with specific preferred embodiments, it should be
understood that the
invention as claimed should not be unduly limited to such specific
embodiments.
The following examples are merely illustrative of the present invention and
should not
be construed to limit the scope of the invention as indicated by the appended
claims in any
way.
EXAMPLES
Example 1: Production of Ether Monocarboxylic Acid
In the following, a general method for producing an ether carboxylic acid of
the invention is
outlined.
Material used: 664,0 g = 1,0 Mol mixture of cetylalcohol + 9 EO (EO =
ethoxy radicals) and
oleylalcohol + 9 E0
122,3 g = 1,05 Mol Na-monochloroacetate
44,0 g = 1,065 Mol NaOH
364,0 g H20
121,2 g = 1,064 Mol HC1 32 %
Equipment: a) 21 stirring apparatus, contact thermometer having a N2-
connector,
steam bath separating funnel
b) 1 1 stirring apparatus with a distillation bridge, contact thermometer,
water jet pump; funnel with filter flask
The ethoxylate was mixed at 45 C with the sodium monochloroacetate and the
resulting
thick suspension was stirred at 45-50 C under N2 for 15 minutes. NaOH was
added in four
portions of 11 g each and stirred each time for 45 minutes. The temperature
was thereby
maintained at 50 - 55 O C.
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Next, the mixture was stirred for 3 h at 70 - 77 C. After the addition of
hydrochloric acid the
mixture was heated to 90 C while slowly stirring the composition.
The product was transferred to a separating funnel and kept for 30 minutes
over a steam bath
to separate the mixture. A clear aqueous solution was separated and kept for
further 15
minutes over the steam bath for a second round of separation. After removal of
the remaining
aqueous phase the organic phase was dried to 104 C under water jet vacuum.
Analysis : acid value : 63,3, saponification value : 65,9, hydroxyl value :
8,7, water content:
8.7%
Example 2: Production of Test-Solutions
A 22 vol% calcium brine solution was made by dissolving 586,7g CaCl2* 2 H20 in
2kg of
distilled water.
The following brine-based drilling fluids have been prepared:
Composition A
22 vol% calcium brine 100 vol% 97,5 vol% 97,5 vol%
solution
Pluronic RPE 1050 0 vol% 2,5 vol% 0 vol%
(block polymer of ethylene
oxide and propylene oxide
with a molar mass of 1950
g/mol)
R-0-(CH2CH20)0CH2COOH 0 vol% 0 vol% 2,5 vol%
wherein R = C16/C18 and
n = 9
Example 3: Testing Biological Degradability
The biodegradation rate was measured using a manometric respirometry test
according to
OECD 301 B, ISO 9439, 92/69 / EEC. The test was performed under aerobic
conditions.
Respirometric BOD-determination is carried out with CO2-absorption on soda
lime. For the
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purpose of the data outlined in the following, biodegradability is expressed
as the percentage
CO2-formation relative to the theoretical value.
The results were as follows:
Compound Pluronic RPE 1050 R-0-
(CH2C1-170).CH2COOH
wherein R = C16/C18 and
n = 9
%CO2 formation >60% 74%
(after 28 days)
Example 4: Determining Lubricant Quality
Lubricity was measured according to method ASTM D 3233A using a Falex pin-and-
vee
block tester.
Compositions A through C were tested. The results are shown in figure 1.
According to these
results the ether monocarboxylic acid of the invention in composition (C)
shows unexpected
and enhanced lubrication properties compared to the control (A) and a prior
art additive (in
composition B). At the same time the ether monocarboxylic acid of the
invention showed a
good biodegradability (see example above).
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